CN104211845A - Terpolymer and thermosetting resin composition thereof - Google Patents

Terpolymer and thermosetting resin composition thereof Download PDF

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CN104211845A
CN104211845A CN201410388442.8A CN201410388442A CN104211845A CN 104211845 A CN104211845 A CN 104211845A CN 201410388442 A CN201410388442 A CN 201410388442A CN 104211845 A CN104211845 A CN 104211845A
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resin
terpolymer
thermosetting resin
hydrogen atom
compositions
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CN104211845B (en
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何继亮
马建
崔春梅
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Suzhou Shengyi Technology Co Ltd
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Suzhou Shengyi Technology Co Ltd
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Abstract

The invention provides a terpolymer containing structural units represented by a general formula (I), a general formula (II) and a general formula (III). The invention also provides a thermosetting resin composition containing the terpolymer and epoxy resin. The composition has low dielectric constant, low dielectric loss tangent, and excellent heat resistance. The invention also provides a prepreg and a laminate prepared from the thermosetting resin composition, and the thermosetting resin composition can be used in printed circuit substrate material and printed circuit board.

Description

A kind of terpolymer and compositions of thermosetting resin thereof
Technical field
The invention belongs to technical field of electronic materials, particularly relate to a kind of terpolymer and comprise the compositions of thermosetting resin of this ter-polymers, and the prepreg using this resin combination to make and veneer sheet.
Background technology
In prior art, be must have good thermotolerance, insulativity, processibility and the advantage such as with low cost by the material prepared of the compositions of thermosetting resin of composition with epoxy resin and solidifying agent thereof, therefore be widely used in, in the electronic material such as semi-conductor, printed circuit board, having become starting material main in printed circuit board.
In recent years, along with the continuous propelling of information processing and information transmission high-speed high frequency technology, in dielectric properties, more and more higher requirement is proposed to tellite material.In simple terms, namely tellite material require possesses lower specific inductivity and dielectric loss tangent, the delay of signal during to reduce high-speed transfer, distortion and loss, and the interference between signal.Therefore, expect to provide a kind of compositions of thermosetting resin, the printed circuit board material using this compositions of thermosetting resin to make can show low-k and low-dielectric loss tangent at the signals transmission of high speed, high frequency.
Styrene-maleic anhydride copolymer has good reactivity worth, and the composition epoxy resin after its solidification has excellent dielectric properties, and therefore, the composition epoxy resin of its solidification is often used to the printed circuit board material making high-frequency high-speed field.
Mention in patent BE627887, use styrene-maleic anhydride copolymer as the solidifying agent of epoxy resin, but the second-order transition temperature degree of the composition epoxy resin after solidification is very low, the requirement to resistance toheat in materials'use process can not be met, also do not meet in the course of processing and more come under unleaded trend to want high heat resistant requirements.
Mention in patent TW552280B, use the styrene-maleic anhydride copolymer that N-substituent maleimide is monomer modified, after this modified resin is used for cured epoxy resin, the second-order transition temperature of composition epoxy resin is increased substantially.But the substituting group on its modified monomer N-substituent maleimide used, with hydroxyl or carboxyl, such meeting produces secondary hydroxyl in the process of cured epoxy resin, make the dielectric properties deterioration of cured article, namely dielectricity constant and dielectric loss increase, with not having the ester group of reactive behavior, making cross-linking set reduce like this, limiting the further raising of resistance toheat.
Therefore, the present invention have developed a kind of terpolymer, and the composition epoxy resin making it solidify has excellent dielectric properties and resistance toheat concurrently simultaneously.
Summary of the invention
For solve prior art provide thermosetting resin poor heat resistance, dielectricity difference or the problems such as good electricity saving performance and resistance toheat can not be possessed simultaneously, the invention provides a kind of new terpolymer and compositions of thermosetting resin thereof, and the prepreg using this resin combination to make and veneer sheet.
For solving the problem, the present invention introduces N-substituent maleimide monomer in styrene-maleic anhydride copolymer, and the substituting group on this N-substituent maleimide monomer is the active ester groups with reactive behavior, thus obtains a kind of terpolymer.The structural unit that the structural unit that described terpolymer contains structural unit that (a) logical formula I represents, (b) logical formula II represents, (c) logical formula III represent;
(I) , in formula, x is positive integer, R in formula 1for the alkyl of hydrogen atom or C1 ~ C5, R 2for the aliphatic alkyl of hydrogen atom, aromatic hydrocarbyl or C1 ~ C5;
(II) , in formula, y is positive integer, R 3, R 4respective independence is the alkyl of hydrogen atom, aromatic hydrocarbyl or C1 ~ C8;
(III) or , in formula, z is positive integer, R 3', R 3", R 4', R 4" independent separately, be the alkyl of hydrogen atom, aromatic hydrocarbyl or C1 ~ C8, R 5for the alkyl of C1-C5 or the cycloalkylidene of C1-C8 or phenylene, R 6be selected from following group:
, , , , , , , , , , , , wherein R 7for the aliphatic alkyl of hydrogen atom, nitro, halogen atom, cyano group, aromatic hydrocarbyl or C1 ~ C5, R 7be preferably hydrogen atom, R 8for the arylalkyl of the alkyl of hydrogen atom, C1-C8, the alkylaryl of C7-C15 or C7-C15, R 8be preferably methyl.
In technique scheme, the R of described terpolymer 6group, preferred maleimide phenoxyl can obtain good resistance toheat, is preferably
or good flame retardant properties can be obtained.
The number-average molecular weight of above-mentioned terpolymer is 1500 ~ 50000g/mol, preferably 3000 ~ 30000g/mol, is more preferably 5000 ~ 20000g/mol.
In technique scheme, in terpolymer, x is 1:1 ~ 15:1 with the ratio of (y+z), and preferred proportion is 1:1 ~ 10:1, more preferably ratio: 1:1 ~ 5:1.
In technique scheme, in terpolymer, the ratio of y and z is 1:10 ~ 10:1, and preferred proportion is 1:5 ~ 5:1.
In technique scheme, described terpolymer can obtain by the following method: the maleimide that first obtained active ester replaces with carrying out esterification under catalyst action with the substituent maleimide of phenol and carboxylic acid, or under catalyst action, carries out the maleimide of esterification and obtained active ester replacement with the maleimide of band carboxylic acid substituent and phenolic hydroxyl-compounds or phenol sulfhydryl compound or hydroxylamine compound.Then, maleimide three kinds of monomer copolymerizables that vinylbenzene, maleic anhydride, active ester replace are obtained terpolymer.Described carboxylic acid can be aliphatic carboxylic acid, aromatic carboxylic acid.Described catalyzer can be an acidic catalyst or basic catalyst, and an acidic catalyst can be phosphoric acid, sulfonic acid, Lewis acid etc., and basic catalyst can be sodium hydroxide, potassium hydroxide, DMAP, amine etc.
The present invention provides a kind of compositions of thermosetting resin simultaneously, comprising:
(1) epoxy resin;
(2) terpolymer,
The structural unit that the structural unit that described terpolymer contains structural unit that (a) logical formula I represents, (b) logical formula II represents, (c) logical formula III represent;
(I) , in formula, x is positive integer, R in formula 1for the alkyl of hydrogen atom or C1 ~ C5, R 2for the aliphatic alkyl of hydrogen atom, aromatic hydrocarbyl or C1 ~ C5;
(II) , in formula, y is positive integer, R 3, R 4respective independence is the alkyl of hydrogen atom, aromatic hydrocarbyl or C1 ~ C8;
(III) or , in formula, z is positive integer, R 3', R 3", R 4', R 4" independent separately, be the alkyl of hydrogen atom, aromatic hydrocarbyl or C1 ~ C8, R 5for the alkyl of C1-C5 or the cycloalkylidene of C1-C8 or phenylene, R 6be selected from following group:
, , , , , , , , , , , , wherein R 7for the aliphatic alkyl of hydrogen atom, nitro, halogen atom, cyano group, aromatic hydrocarbyl or C1 ~ C5, R 8for the arylalkyl of the alkyl of hydrogen atom, C1-C8, the alkylaryl of C7-C15 or C7-C15; In its epoxy group and terpolymer, the molar ratio of acid anhydrides and ester group total amount is 1:5 ~ 4:1, and preferred proportion is 3:5 ~ 2:1.The number-average molecular weight of described terpolymer is 1500 ~ 50000g/mol, preferably 3000 ~ 30000g/mol, is more preferably 5000 ~ 20000g/mol.
In technique scheme, in terpolymer, x is 1:1 ~ 15:1 with the ratio of (y+z), and preferred proportion is 1:1 ~ 10:1, and more preferably ratio is 1:1 ~ 5:1.In technique scheme, in terpolymer, the ratio of y and z is 1:10 ~ 10:1, and preferred proportion is 1:5 ~ 5:1.
In technique scheme, described component (1) epoxy resin can be selected from bisphenol A epoxide resin, bisphenol F epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, phenol novolac epoxy resins, cresol novolak epoxy, triphenyl methane epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate-based epoxy resin, aralkyl novolac epoxy resin, alicyclic based epoxy resin, glycidyl amine type epoxy resin, in glycidyl ester type epoxy resin one or more.
Preferably, described component (1) epoxy resin is selected from one or more in biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl novolac epoxy resin, phosphorous epoxy resin.
In technique scheme, compositions of thermosetting resin can also comprise the solidifying agent such as amine compound, acid amides based compound, acid anhydrides based compound, phenol system compound, cyanate as co-curing agent.Specifically, amine system solidifying agent can be diaminodiphenyl-methane, diaminodiphenylsulfone(DDS), diethylenetriamine, bismaleimides, two carboxyl phthalic imidine, imidazoles etc.; Acid amides based compound can be Dyhard RU 100, Versamid etc.; Acid anhydrides based compound can be Tetra hydro Phthalic anhydride, trimellitic anhydride, pyromellitic acid anhydride, maleic anhydride, hydrogenated phthalic anhydride, carbic anhydride etc.; Phenol system compound can be phosphorus containing phenolic resin, Nitrogen-containing Phenolic Resins, bisphenol A phenolic resin, phenol novolacs, naphthol novolac resin, biphenyl modified phenolic resins, biphenyl modification naphthol resin, dicyclopentadiene phenol add-on type resin, phenol aralkyl resin, naphthols aralkyl resin, Pehanorm resin, benzoxazine colophony etc.
Preferably, the co-curing agent in the compositions of thermosetting resin of technique scheme is selected from following resin: bimaleimide resin, cyanate ester resin, naphthol novolac resin, biphenyl modified phenolic resins, biphenyl modification naphthol resin, dicyclopentadiene phenol add-on type resin, phosphorus containing phenolic resin.
Preferably, add cyanate ester resin as co-curing agent in the compositions of thermosetting resin of technique scheme, and the weight ratio of cyanate ester resin and component (1) epoxy resin is 100:20 ~ 100:300, preferred proportion is 100:50 ~ 100:200.Described cyanate ester resin can be selected from one or more in bisphenol A cyanate ester resin, Bisphenol F cyanate ester resin, bis-phenol M cyanate ester resin, dicyclopentadiene type ethylene rhodanate resin, o-cresol aldehyde type epoxy resin, phenol type cyanate ester resin.
Preferably, bimaleimide resin is added as co-curing agent in the compositions of thermosetting resin of technique scheme, and the weight ratio of bimaleimide resin and component (2) terpolymer is 100:20 ~ 100:300, preferred proportion is 100:50 ~ 100:150, wherein R in terpolymer 6group is preferably maleimide phenoxyl.Described bimaleimide resin is allyl group modified bismaleimide resin, and its number-average molecular weight is 1000 ~ 8000g/mol, preferably 2000 ~ 5000g/mol.
In technique scheme, described compositions of thermosetting resin can further include toughner, fire retardant, mineral filler and curing catalyst.
Described toughner can be high molecular phenoxy resin, rubber etc.
Described fire retardant can be bromide fire retardant, phosphorus flame retardant, nitrogenated flame retardant, organic silicon fibre retardant, organic metal salt fire retardant, inorganic flame retardant etc.Wherein, bromide fire retardant can be decabromodiphynly oxide, TDE, brominated styrene or tetrabromo-phthalic diformamide.Phosphorus flame retardant can be the general organophosphorus based compounds and 9 such as inorganic phosphorus, phosphate compound, phosphinic acid compounds, phosphinic compounds, phosphine oxide compound, organic system Nitrogen-and Phosphorus-containing compound, 10-dihydro-9 oxa--10-phosphine is mixed phenanthrene-10-oxide compound, 10-(2,5 dihydroxy phenyls)-9, mix phenanthrene-10-oxide compound, 10-phenyl-9,10-dihydro-9-oxy of 10-dihydro-9 oxa--10-phosphine is mixed the organophosphorus compound of the DOPO structures such as-10-phosphine phenanthrene-10-oxide compound and the derivative etc. that uses itself and the compound such as epoxy resin, resol to react.Nitrogenated flame retardant can be triaizine compounds, cyanuric acid compound, isocyanic acid compound, thiodiphenylamine etc.Organic silicon fibre retardant can be organic silicone oil, organo-silicone rubber, silicone resin etc.Organo-metallic fire retardant can be ferrocene, acetylacetone metal complex, organo-metallic carbonyl compound etc.Inorganic flame retardant can be aluminium hydroxide, magnesium hydroxide, aluminum oxide, barium oxide etc.
The content of described mineral filler amounts to 100 weight parts relative to compositions of thermosetting resin, is 5 ~ 300 weight parts, is preferably 5 ~ 80 weight parts.Described mineral filler is selected from one or more in powdered quartz, fused silica, preparing spherical SiO 2, aluminum oxide, aluminium hydroxide, aluminium nitride, boron nitride, titanium dioxide, strontium titanate, barium titanate, barium sulfate, talcum powder, Calucium Silicate powder, calcium carbonate, mica, tetrafluoroethylene.
Described curing catalyst adds use according to practical situation, can be selected from dimethyl aminopyridine, tertiary amine and salt thereof, imidazoles, organic metal salt, triphenylphosphine Ji Qi phosphonium salt etc.
In technique scheme, in described compositions of thermosetting resin, can also add according to actual feelings additives such as using silane coupling agent, pigment, emulsifying agent, dispersion agent.
Above-mentioned compositions of thermosetting resin, may be used for manufacturing semiconductor-encapsulating material, lamination adhering film, binding agent, resin cast material, conductive paste etc.
Present invention also offers the prepreg adopting above-mentioned resin combination to make, above-mentioned resin combination dissolution with solvents is made glue, then strongthener is immersed in above-mentioned glue; After flooding after strongthener heat drying, described prepreg can be obtained.
One or more in described solvent selected from acetone, butanone, toluene, mibk, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, ethylene glycol monomethyl ether, propylene glycol monomethyl ether.Described strongthener refers to the base material of prepreg of the present invention, can be suitable for the well known materials may used in various veneer sheet, such as natural fiber, organic synthetic fibers, organic fabric or inorganic fabric, and their mixture.
Be immersed in by strongthener in glue, then heat drying, heat drying 1-30 minute at the temperature of 100-200 degree, makes it semicure usually.
Present invention also offers the veneer sheet adopting above-mentioned resin combination to make, be covered with tinsel at one by the single or double of above-mentioned prepreg, or after being superposed at least 2 by above-mentioned prepreg, be covered with tinsel at its single or double, hot compacting, can obtain described veneer sheet.
The quantity of described prepreg is that laminate thickness is as requested determined, available one or more.Described tinsel, as long as the material used in electrically insulating material purposes, is not particularly limited, and can be Copper Foil, also can be aluminium foil, and their thickness is not particularly limited.In addition, molding condition is applicable electrically insulating material veneer sheet and multiple-plate method such as, such as, can use multiple deck press, multi-layer vacuum press, continuous molding, hot compacting machine etc., at temperature 100-250 DEG C, pressure 2-100kg/cm 2, 0.1-5 hour heat-up time scope internal shaping.
Beneficial effect of the present invention: resin combination of the present invention not only has excellent dielectric properties, but also there is excellent resistance toheat.The veneer sheet obtained by compositions of thermosetting resin of the present invention has excellent dielectric properties, compared with prior art, specific inductivity and dielectric loss all decline to a great extent, and can show fully low low-k and low-dielectric loss tangent at the signals transmission of high speed, high frequency.
Embodiment
To be further described by specific embodiment below.But should be appreciated that specific embodiment only for explaining the present invention, the protection domain be not intended to limit the present invention.Instrument, equipment, reagent, method etc. used in the application, as do not specialized, are instrument, equipment, reagent and method that this area is conventional.When without special instruction, " part " representative " weight part ", " % " representative " % by weight ".Embodiment 1 ~ 5 is synthesis of terpolymer of the present invention, and embodiment 6 ~ 7 is band carboxyl or the synthesis of polymkeric substance of ester group of reactive behavior of not having, and embodiment 8 ~ 13 and embodiment 14 ~ 15 are preparation and the performance evaluation of compositions of thermosetting resin.
Embodiment 1
By N-(4 hydroxy phenyl) maleimide 95g(0.5mol), dicyclohexylcarbodiimide 110g(0.53mol), acetic acid 30g(0.5mol) be fully dissolved in ethyl acetate and be placed in three neck reaction flasks and fully mix, then 1.20g4-Dimethylamino pyridine is under agitation added, then cool for some time under reacting low temperature environment reaction soln being placed in after 6 hours 0 ~ 5 DEG C under room temperature filters to isolate solid impurity, then that the distillation of obtained product, purifying is obtained to dimaleoyl imino phenethyl ester.Then, dimaleoyl imino phenethyl ester 78g(0.33mol by obtained above), vinylbenzene 830g(8.0mol), maleic anhydride 176g(1.80mol) be fully dissolved in butanone, add 50g benzoyl peroxide initiator and 80g amylene chain-transfer agent, react 3 hours and obtained terpolymer (A-1) under 70 ~ 90 DEG C of conditions, use GPC method to record its number-average molecular weight for 4900g/mol, in its structural formula, comprise following three kinds of structural units:
（Ⅰ） ，（Ⅱ） ，（Ⅲ）? ，
In formula, x, y, z is positive integer, and the ratio of x and (y+z) is the ratio of 3.8:1, y and z is 5.5:1, R1, R2, R3, R4, R3 ", R4 " be hydrogen atom, R8 is methyl.
Embodiment 2
Obtained dimaleoyl imino phenethyl ester as in Example 1.Then, dimaleoyl imino phenethyl ester 350g(1.50mol by obtained above), vinylbenzene 1040g(10.0mol), maleic anhydride 33g(0.33mol) be fully dissolved in butanone, add 55g benzoyl peroxide initiator and 120g amylene chain-transfer agent, react 4 hours and obtained terpolymer (A-2) under 70 ~ 90 DEG C of conditions, GPC method is used to record its number-average molecular weight for 7500g/mol, its structure is with embodiment 1, the ratio that x is 5.5:1, y and z with the ratio of (y+z) is 1:5.
Embodiment 3
By N-(4 carboxyl phenyl) maleimide 108g(0.5mol), dicyclohexylcarbodiimide 110g(0.53mol), phenol 50g(0.53mol) be fully dissolved in ethyl acetate and be placed in three neck reaction flasks and fully mix, then 2.0g4-Dimethylamino pyridine is under agitation added, react under room temperature after 6 hours, then cool for some time under reaction soln being placed in the low temperature environment of 0 ~ 5 DEG C filters to isolate solid impurity, then that the distillation of obtained product, purifying is obtained to dimaleoyl imino phenylamino benzoic acid phenolic ester.Then, by obtained to dimaleoyl imino phenylamino benzoic acid phenolic ester 193g(0.66mol above), vinylbenzene 312g(3.0mol), maleic anhydride 33g(0.33mol) be fully dissolved in butanone, add 20g benzoyl peroxide initiator and 50g amylene chain-transfer agent, react 5 hours and obtained terpolymer (A-3) under 70 ~ 90 DEG C of conditions, use GPC method to record its number-average molecular weight for 11500g/mol, in its structural formula, comprise following three kinds of structural units:
（Ⅰ） ，（Ⅱ） ，（Ⅲ） ，
In formula, x, y, z is positive integer, and the ratio of x and (y+z) is the ratio of 3:1, y and z is 1:2, R1, R2, R3, R4, R3 ', R4 ' is hydrogen atom, R5 is phenylene, and R6 is phenoxy group.
Embodiment 4
By N-(4 carboxyl phenyl) maleimide 108g(0.5mol), dicyclohexylcarbodiimide 110g(0.53mol), 3-hydroxyl-1,2,3-phentriazine-4 (3H)-one 85g(0.52mol) be fully dissolved in ethyl acetate and be placed in three neck reaction flasks and fully mix, then 5.0g4-Dimethylamino pyridine is under agitation added, after reacting 8 hours under room temperature, then cool for some time under reaction soln being placed in the low temperature environment of 0 ~ 5 DEG C filters to isolate solid impurity, then that the distillation of obtained product, purifying is obtained to maleimidobenzoate.Then, by obtained to maleimidobenzoate 120g(0.33mol above), vinylbenzene 208g(2.0mol), maleic anhydride 66g(0.67mol) be fully dissolved in butanone, add 15g benzoyl peroxide initiator and 35.0g amylene chain-transfer agent, react 5 hours and obtained terpolymer (A-4) under 70 ~ 90 DEG C of conditions, use GPC method to record its number-average molecular weight for 15400g/mol, in its structural formula, comprise following three kinds of structural units:
（Ⅰ） ，（Ⅱ） ，（Ⅲ） ?，
In formula, x, y, z is positive integer, and the ratio of x and (y+z) is the ratio of 2:1, y and z is 2:1, R1, R2, R3, R4, R3 ', R4 ' is hydrogen atom, R5 is phenylene, and R6 is .
Embodiment 5
By N-(4 carboxyl phenyl) maleimide 108g(0.5mol), dicyclohexylcarbodiimide 110g(0.53mol), N-(4 hydroxy phenyl) maleimide 95g(0.52mol) be fully dissolved in ethyl acetate and be placed in three neck reaction flasks and fully mix, then 3.0g4-Dimethylamino pyridine is under agitation added, after reacting 8 hours under room temperature, then cool for some time under reaction soln being placed in the low temperature environment of 0 ~ 5 DEG C filters to isolate solid impurity, then that the distillation of obtained product, purifying is obtained to maleimidobenzoate.Then, by obtained to maleimidobenzoate 194g(0.50mol above), vinylbenzene 104g(5mol), maleic anhydride 49g(0.50mol) be fully dissolved in butanone, add 10g benzoyl peroxide initiator and 25.0g Dodecyl Mercaptan chain-transfer agent, react 7 hours and obtained terpolymer (A-5) under 70 ~ 90 DEG C of conditions, use GPC method to record its number-average molecular weight for 20500g/mol, in its structural formula, comprise following three kinds of structural units:
（Ⅰ） ，（Ⅱ） ，（Ⅲ） ，
In formula, x, y, z is positive integer, and the ratio of x and (y+z) is the ratio of 1:1, y and z is 1:1, R1, R2, R3, R4, R3 ', R4 ' is hydrogen atom, R5 is phenylene, R6 maleimide phenoxyl.
Embodiment 6
Get vinylbenzene 104g(1mol), maleic anhydride 49g(0.5mol), N-(4 carboxyl phenyl) maleimide 108g(0.5mol) be fully dissolved in butanone, add 9.8g benzoyl peroxide initiator and 25.0g amylene chain-transfer agent, react 6 hours and obtained terpolymer (B-1) under 70 ~ 90 DEG C of conditions, use GPC method to record its number-average molecular weight for 8000g/mol, in its structural formula, comprise following three kinds of structural units:
（Ⅰ） ，（Ⅱ） ，（Ⅲ） ?，
In formula, x, y, z is positive integer, and the ratio of x and (y+z) is the ratio of 1:1, y and z is 1:1, R1, R2, R3, R4, R3 ', R4 ' is hydrogen atom, R5 is phenylene, and R6 is hydroxyl.
Embodiment 7
By N-(4 carboxyl phenyl) maleimide 108g(0.5mol), dicyclohexylcarbodiimide 110g(0.53mol), methyl alcohol 16g(0.50mol) be fully dissolved in ethyl acetate and be placed in three neck reaction flasks and fully mix, then the DMAP of 1.20g is under agitation added, after reacting 6 hours under room temperature, then cool for some time under reaction soln being placed in the low temperature environment of 0 ~ 5 DEG C filters to isolate solid impurity, then that the distillation of obtained product, purifying is obtained to maleimidobenzoate.。Then, by obtained to dimaleoyl imino methyl benzoate 77g(0.33mol above), vinylbenzene 70g(0.67mol), maleic anhydride 33g(0.33mol) be fully dissolved in butanone, add 6.5g benzoyl peroxide initiator and 20.0g amylene chain-transfer agent, react 7 hours and obtained terpolymer (B-2) under 70 ~ 90 DEG C of conditions, use GPC method to record its number-average molecular weight for 10000g/mol, in its structural formula, comprise following three kinds of structural units:
（Ⅰ） ，（Ⅱ） ，（Ⅲ） ?，
In formula, x, y, z is positive integer, and the ratio of x and (y+z) is the ratio of 1:1, y and z is 1:1, R1, R2, R3, R4, R3 ', R4 ' is hydrogen atom, R5 is phenylene, and R6 is methoxyl group.
Embodiment 8-15
According to the formula that table 1 is recorded, all components is mixed with the resin adhesive liquid that solid content is 60%, curing catalyst adds according to the amount of 0.5phr.
Then veneer sheet is made under the following conditions, and by following method evaluation flame retardant resistance, wet-hot aging performance and dielectric characteristics.The results are shown in table 1.
< veneer sheet manufacturing conditions >
Base material: ordinary electronic level 2116 glass-fiber-fabric;
The number of plies: 5;
Shaping rear sheet metal thickness: 1.0mm;
Preimpregnation semicure condition: 165 DEG C/5min;
Condition of cure: 150 DEG C/60min+200 DEG C/120min;
< thermotolerance > second-order transition temperature (Tg) characterizes thermotolerance, according to dsc, measures according to the DSC method of IPC-TM-650 2.4.25 defined.
The mensuration > specific inductivity of < specific inductivity and dielectric loss tangent uses flat band method according to IPC-TM-650 2.5.5.9, measures the specific inductivity under 1GHz; Dielectric loss tangent: use flat band method according to IPC-TM-650 2.5.5.9, measures the dielectric loss factor under 1GHz.
< flame retardant resistance > measures according to UL94 method.Not fire-retardantly to represent with " No ".
Table 1
The explanation of table 1:
A-1: terpolymer (A-1) obtained in embodiment 1;
A-2: terpolymer (A-2) obtained in embodiment 2;
A-3: terpolymer (A-3) obtained in embodiment 3;
A-4: terpolymer (A-4) obtained in embodiment 4;
A-5: terpolymer (A-5) obtained in embodiment 5;
B-1: terpolymer (B-1) obtained in embodiment 6;
B-2: terpolymer (B-2) obtained in embodiment 7;
Epoxy resin 1: dicyclopentadiene type resol, chemical drug, epoxy equivalent (weight) 265g/eq;
Epoxy resin 2: phosphorous epoxy resin, CHIN YEE PE-315, epoxy equivalent (weight) 300g/eq, phosphorus content 3.5%wt;
Equivalence ratio: the equivalence ratio of active ester groups in epoxy group(ing) and upgrading type Zelan 338;
Cyanate: bisphenol A cyanate ester resin, Lonza, BA-3000S;
Bismaleimides: self-control allyl group modified BMI resin prepolymer, synthetic method is by 100 parts of bimaleimide resins and 50 parts of allylic cpds, at 130 degree of temperature, react 85min, be cooled to room temperature after reaction terminates and obtain, its number-average molecular weight is 3500g/mol;
Phosphorus-containing phenolic aldehyde: Dow 92741 phosphorus content 9.2%wt;
Toughner: nucleocapsid particles toughner, EVONIK;
Curing catalyst: 2-methyl-4-ethyl imidazol(e);
Filler: silicon-dioxide.
From upper table 1, what embodiment 8 ~ 13 adopted is terpolymer cured epoxy resin in the present invention, compare the embodiment 14 of the styrene-maleic anhydride copolymer cured epoxy resin of the N-substituent maleimide modification using band carboxyl, significantly reduce the low-k after epoxy resin cure, low-dielectric loss tangent.The embodiment 15 of the styrene-maleic anhydride copolymer cured epoxy resin of the N-substituent maleimide modification of embodiment 8 ~ 13 and the common ester group of use band, has higher second-order transition temperature, obtains excellent resistance toheat.Embodiment 12 with the addition of the resin system of cyanate ester resin as co-curing agent, compares embodiment 8 ~ 11, have more excellent resistance toheat and dielectric properties.Embodiment 13 with the addition of the resin system of bimaleimide resin as co-curing agent, compares embodiment 8 ~ 11, have more excellent resistance toheat and dielectric properties.

Claims (10)

1. a terpolymer, is characterized in that, the structural unit that the structural unit that described terpolymer contains structural unit that (a) logical formula I represents, (b) logical formula II represents, (c) logical formula III represent;
, in formula, x is positive integer, R in formula 1for the alkyl of hydrogen atom or C1 ~ C5, R 2for the aliphatic alkyl of hydrogen atom, aromatic hydrocarbyl or C1 ~ C5;
, in formula, y is positive integer, R 3, R 4respective independence, can be identical or different, is the alkyl of hydrogen atom, aromatic hydrocarbyl or C1 ~ C8;
, in formula, z is positive integer, R 3', R 3", R 4', R 4" independent separately, be the alkyl of hydrogen atom, aromatic hydrocarbyl or C1 ~ C8, R 5for the alkyl of C1-C5 or the cycloalkylidene of C1-C8 or phenylene, R 6be selected from following group:
, , , , , , , , , , , , wherein R 7for the aliphatic alkyl of hydrogen atom, nitro, halogen atom, cyano group, aromatic hydrocarbyl or C1 ~ C5, R 8for the arylalkyl of the alkyl of hydrogen atom, C1-C8, the alkylaryl of C7-C15 or C7-C15, the number-average molecular weight of described terpolymer is 1500 ~ 50000g/mol.
2. terpolymer according to claim 1, is characterized in that, described R 6for maleimide phenoxyl,
or .
3. terpolymer according to claim 1, is characterized in that, the x of described terpolymer and the ratio of (y+z) are 1:1 ~ 15:1, and the ratio of described y and z is 1:10 ~ 10:1.
4. a compositions of thermosetting resin, comprising:
(1) epoxy resin;
(2) terpolymer described in any one of claim 1-3,
In its epoxy group and terpolymer, the molar ratio of acid anhydrides and ester group total amount is 1:5 ~ 4:1.
5. compositions of thermosetting resin according to claim 4, it is characterized in that, described compositions of thermosetting resin also comprises co-curing agent, described co-curing agent is selected from amine compound, acid amides based compound, acid anhydrides based compound, phenol system compound, cyanate, preferably at least one in bimaleimide resin, cyanate ester resin, naphthol novolac resin, biphenyl modified phenolic resins, biphenyl modification naphthol resin, dicyclopentadiene phenol add-on type resin, phosphorus containing phenolic resin.
6. compositions of thermosetting resin according to claim 5, is characterized in that, described co-curing agent is cyanate ester resin, and the weight ratio of cyanate ester resin and epoxy resin is 100:20 ~ 100:300.
7. compositions of thermosetting resin according to claim 5, is characterized in that, described co-curing agent is bimaleimide resin, and the weight ratio of bimaleimide resin and terpolymer is 100:20 ~ 100:300.
8. the compositions of thermosetting resin according to any one of claim 4 ~ 7, is characterized in that, also comprises toughner, fire retardant, mineral filler and curing catalyst.
9. a prepreg, is characterized in that, the resin combination dissolution with solvents described in any one of claim 4 ~ 8 is made glue, is then immersed in by strongthener in above-mentioned glue; After the strongthener heat drying after dipping, described prepreg can be obtained.
10. a veneer sheet, is characterized in that, is covered with tinsel at the single or double of a prepreg according to claim 9, or after at least 2 prepregs superpositions according to claim 9, be covered with tinsel at its single or double, hot compacting, described veneer sheet can be obtained.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106221126A (en) * 2016-08-29 2016-12-14 苏州生益科技有限公司 A kind of compositions of thermosetting resin and use its prepreg made and laminate
CN106243626A (en) * 2016-08-29 2016-12-21 苏州生益科技有限公司 A kind of compositions of thermosetting resin and use its prepreg made and laminate

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001019744A (en) * 1999-06-30 2001-01-23 Ind Technol Res Inst Curing agent used for epoxy resin

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001019744A (en) * 1999-06-30 2001-01-23 Ind Technol Res Inst Curing agent used for epoxy resin

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106221126A (en) * 2016-08-29 2016-12-14 苏州生益科技有限公司 A kind of compositions of thermosetting resin and use its prepreg made and laminate
CN106243626A (en) * 2016-08-29 2016-12-21 苏州生益科技有限公司 A kind of compositions of thermosetting resin and use its prepreg made and laminate

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